DE2241483A1 - CHEMICALLY MODIFIED POLYMERS - Google Patents

Description

224U83

PATENT ANW Ιΐ, ΐΤΕ

ing. THANKS TO H. INTEGTS ■ dipl.-ing. H. HAUCK dipx.-fhys. W. SCHMITZ DIPi ₁₁ -ING. E. GRAALFS · DiPi ₁₁ -ING. W. WEHNERT

HAMBURG-MUNICH ASSIGNMENT ADDRESS: HAMBITHGSe IVKITKR WALI, 41

TSIi. 30 74 28 AND 30 41 13 TELEQR. NEOEDAPATKNT HAM] JUKQ

Owens-Illinois Inc. Munich is · mozartsth. as

Toledo, Ohio 43601 / USA. «.....« β.

TBIiEQH. NEQBUAPATENT MUNICH

Hamburg, 21. August 1972

Chemically modified polymers

The invention relates to the production of new polymeric materials by the chemical modification of Polyolefins, olefin copolymers and other polymers Substances whose structure contains saturated aliphatic hydrocarbon atoms.

The resulting modified polymers are very useful for coating, gluing and "packaging" applications.

A method for producing chemically modified polyolefins or their copolymers is proposed in which an olefin polymer having an ooreactant is brought to reaction, the structure of which has both a hydrocarbon radical and at least one contains highly polar functionalθ group, these

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Reaction is carried out in the presence of a source, which in the presence of heat, light, oxygen, ionizing radiation, etc. to generate free radicals.

More specifically, the present invention relates to the chemical combination of a polyolefin, polymer or copolymer, with one or more non-polymeric organic compounds which have the general formula RX, where R is a linear, branched, or cyclic aliphatic hydrocarbon radical having at least 6 carbon atoms and X is a polar functional group which is a member of the series having the following groups: hydroxyl (-0H);
Carboxyl (-GOOH);
Amide (-GOIm ₂ );

Mono or disubstituted amide: (-0OiIHR ₁ ο lor C0M.R “), where the substituents R. and R _{9 are} the same or different low molecular weight alkyls which contain 1 to 4 carbon atoms;

Amino (-HH);

Ilono- or disubstituted amino (-MIR. Or NR ₁ Rp), where the iJubstituenten R ₁ and

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R are identical or different low molecular weight alkyls containing 1 to 4 carbon atoms; _n -D

OR ₁

Trialkoxysilyl (-SiAoR ₀ ), where the substituents

i
R, R ₂ and R are low molecular weight alkyls containing 1 to 4 carbon atoms; Sulfonic acid (-SOJI); and
Dihydrogen phosphate (-

The group can also carry one or more positive or negative charges, as in the case of the following groups:

Carboxylate (-C0O®);

Sulfonate (-SO ©);

singly charged sulfate (-0S0 ®); singly or doubly charged phosphate (-0P0 H

or -ΟΡΟ®);

Ammonium (M ₁ R ₂ R,), where the substituents R., R ₂ and R are hydrogen or low molecular weight alkyls which contain 1 to 6 carbon atoms;

Sulfonium (-SR ₁ R ₂ ), where the substituents R .., R are identical or different alkyl radicals containing 1 to 6 carbon atoms; and

Phosphonium (PR ₁ R ₂ R), where the substituents

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H ₁ , It and H are the same or different alkyl radicals containing 1 to 6 carbon atoms.

In the Pal3 of such invited groups it goes without saying that at the same time an ion with the opposite jiadiation is present. For example, a sodium ion in the case of a carboxylate or sulfonate group, and a halide ion in the case of an ammonium-sulfonium or phosphonium group.

It is also contemplated that the Ooreactant RX aromatic or heterocyclic rings alB part of the Structure of R, in addition to the essential aliphatic hydrocarbon group or groups. Furthermore, it should be understood that more than one group of the IDype R and / or more than one Type X groups per molecule of the co-reactant RX can be present.

It is also provided that an anhydride or imide with a long-chain alkyl or alkenyl sub substituents, like for example. Dodecenyl succinic anhydride or the corresponding imide, can be used as the RX coreactant.

Compounds of the type RX described here above, in particular those with a single group of type R and a single group of type X

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because of their surface-active properties in general referred to as "surfactants".

According to the present invention, the chemical Combination of the polymeric polyolefin and the non-polymeric co-reactant (EX) effected by subject a mixture of these two substances, optionally in the presence of additional substances, to conditions, which are conducive to the formation of free radicals.

Under such conditions, free radicals derived from the polymer as well as other Formed free radicals derived from the non-polymeric reactant? chemical bonds between the Polymers and the ooreactant arise as a result of radical-radical combination processes (radical chain mechanisms). ·

The formation of cross-linked polymers through processes which involve the formation and mutual reaction of free radical intermediates already state of the art. In such processes occurs as a result of the combination of polymeric radicals a crosslinking between polymeric chains. Typically this is accomplished by having a Mixture of a polymer and an organic peroxide heated so high that the peroxide in free radials disintegrates.

The formation of graft copolymers by d.en

Rad ikaiket benniochan Lsmu «iat is also known. In In such processes, a polymeric radical is formed and goes an addition reaction with the reactive carbon-carbon double bond of a vinyl monomer such as styrene or Methacrylic acid methyl ester.

The resulting radical then adds further vinyl monomer units by successive radical add it ion reactions.

Typical of the formation of such graft copolymers is the heating of a mixture of a polymer, a vinyl monomer and an organic peroxide up to a temperature at which the peroxide decomposes with the formation of free radicals. Likewise is the production of pharmaceutical mixtures of polymers with types of non-polymeric additives of the RX type prior art. Typically be Such additives are used to achieve antistatic properties or to disperse particles To support materials in polymers or polymer solutions

A wide variety of reactor conditions can be used in the practice of the invention described herein can be used to promote the formation of free radicals. In particular, heat, light, oxygen ι substances that initiate the formation of free radicals,

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ionizing rays, U3w. can be used individually or in combination.

In a preferred embodiment of the present invention is a mixture of one Polyolefin or olefin copolymers, a fatty acid and an organic peroxide "up to a sufficiently high Heated temperature that causes decomposition of the peroxide.

In the EaIl of this preferred embodiment are in the following examples of the Polyraer reactants, the fatty acid and peroxide indicated.

Examples of polymer reactants include:

Polyethylene; . .

Polypropylene;

Poly (I-butene);

Poly (-4-methyl-1-pentene); Ethylene-propylene copolymers; Ethylene-1-butene copolymers j Ethylene-1-hexene copolymers; Ethylene vinyl acetate copolyraere; Ethylene-ethyl acrylate copolymers; and Ethylene-acrylic acid oil copolymers.

Examples of fatty acids include: caproic acid;

lauric acid;

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Stearic acid;

Palmitic acid;

Myristic acid;

Arachidic acid;

Behenic acid;

oleic acid;

Linoleic acid;

Linolenic acid;

Eleostearic acid;

Ricinoleic acid;

Erucic acid;

Elaidic acid; and

Arocnidonic acid.

Examples of peroxides include:

Acetyl peroxide; Benzoyl peroxide; p-chlorobenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; Ditoluoyl peroxide; Decanoyl peroxide; Lauryl peroxide; Isobutyryl peroxide, diisononanoyl peroxide; Pelargonyl peroxide; Tert-butyl peroxyacetate; Tert-butyl peroxymaleic acid; Tert-butyl peroxyisobutyrate; Tert-butyl peroxypivalate, tert-butyl peroxybenzoate; Tert-butyl peroxycrotonate; Tert-butyl peroxy (2-ethyl hexanoate); 2,5-dimethyl-2,5-bis (- 2-ethylhexanoylperoxy) -hexane; 2,5-mmettayl-2,5-bis (benzoylperoxy) hexane; 2,5-methyl-2,5-bis-

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(tert-butylperoxy) hexane; 2,5-dimethyl-2,5-bis (tert-butylperoxy) -hexane-3; Di-ter-t-butyl-diperoxyphthalate 1 .1.3.3-tetramethylbutylperoxy-2-ethyl-hexanoate; Di-tert-butyl peroxide; Di-tert-amyl peroxide; Tertiary amyl tertiary butyl peroxide; 1.1-di-tert. butylperoxy-3,3,5-trimethylcyclohexane; Bis (tert-butylperoxy) diisopropylbenzene; Butyl-4> 4-bis (tert.bufcylperoxy) valerate, dieumyl peroxide; Acetylacetone peroxide; Methyl ethyl ketone peroxide; cyclohexanone peroxide; Tert. Butylperoxyisopropylcarbonatj 2,2-bis (tert «butylperoxy) butane; Di (2-ethylhexyl) peroxydicarbonate; uuü Bia- (4-tert-butylcyclohexyl) peroxydicarbonate.

In a second special embodiment, a Mixture of an olefin polymer or co-polymer, a organic peroxide and a long chain alcohol, amine, or amine oxide to a sufficiently high one Heated temperature that causes thermal decomposition of the peroxide. About the suitable polymeric reactants and peroxides include the substances mentioned in the first embodiment. Suitable co-reactants include Alcohols such as lauryl alcohol, stearyl alcohol, Cetyl alcohol and oleyl alcohol, amines such as lauryl dimethylamine, Stearyl dimethylamine and stearylamine; and Amine oxides such as liauryl-dimethylamine oxide, stearyl dimethylamine oxide and Oetyldimethylaminoxia »

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In a third embodiment, a mixture of an olefin polymer or Odpolymeren, an organic peroxide and a nonionic, cationic or anionic surfactant is heated to a temperature which is sufficient to cause thermal decomposition of the peroxide. Suitable polymeric reactants and peroxides include the substances mentioned in the text of the first embodiment. Surfactants which are suitable as coreactants are listed below.

Examples of nonionic surfactants include nonylphenol ethylene oxide condensation products; Octylphenol ethylene oxide condensation products; Mono- and diglycerides, for example monostearin, Distearin, honoolein, diolein; and polyethylene glycol and derivatives, including the fatty acid ester (mono- and di-).

Examples of cationic surfactants include: lauryl trimethylammonium chloride; lauryl pyridinium chloride;
Cetyl trimethylammonium bromide; Getyl pyridinium bromide;
Oetyl-pyridinium chloride;
Cetyl-dimethylbenzylammonium chloride; Stearyl dimethylbenzyl ammonium chloride; and dilauryldimethylammonium bromide. 309810/0998

Examples of anionic surfactants include: ITatr iumlaurate;
llatriurastearate;
ITatr iumoleate;
ITatr iuralauryl sulfate;
latrium dioctyl sulfosuccinate; Sodium dinonyl sulfosuccinate; Sodium dodecylbenzenesulfonate and iauryl acid phosphate.

In a fourth special embodiment, a mixture of an olefin polymer or copolymer, an organic peroxide and a resin acid or its salt, or an aliphatic dicarbon or tricarbon

Otr

acid Qy 'heats its salt to a temperature sufficient to cause thermal decomposition of the peroxide. Suitable polymeric reactants and peroxides include the "substances mentioned in the first embodiment."

To geei, '_, netp.u carboxyl-containing reactants and salts include resin acids and salts such as abietic acid, levopimaric acid, Calcium salts of resin acids, barium salts of resin acids and sodium salts of resin acids; Dicarboxylic acids and salts such as dimer acids, sebacic acid, azelaic acid and ITodium sebacate; as well as tricarboxylic acids like trimeric acids.

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In a fifth specific embodiment, a Mixture of an olefin polymer or copolymer, a organic peroxide and an iettsäureamid heated to a temperature that is sufficient to thermal To cause decomposition of the peroxide. Suitable polymeric reactants and peroxides include those in first execution of the substances described in the Gbrm.

Suitable fatty acid amides include: oleic acid diethanolamide;
Lauric acid diethanolamide;
Stearic acid iethynolamide;
Lauric acid-NjN-dimethylamide and stearic acid-NjN-dimethylamide.

In some or all of the foregoing embodiments, instead of a single compound, a Mixtures of two or more coreactants of the RX type can be used.

In some or all of the foregoing embodiments, the organic peroxide can be by a other reagent or combination of reagents which are capable of generating free radicals under suitable conditions. Such reagents include the following:

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Hydroperoxides

tert-butyl hydroperoxide

Cumene hydroperoxide

Diisopropylbenzene hydroperoxide

2,5-imethylhexane-2,5-dl hydroperoxide.

p-menthane hydroperoxide

1,1,3,3-tetramethyrbutyl hydroperoxide.

Organometallic compounds, alone or in Combination with hydroperoxides can be used:

Cobalt-2-ethylhexanoate cobalt-2-haphthenate Cobalt tallate copper naphthenate copper phthalocyanine Copper ac etylaceton ferric acetylacetone Ferrous Acetyl Acetone Iron (II) stearate Iron neodecanoate Iron talate Manganese naphthenate Manganese tallat.

Azo compounds

isobutyronitrile) 2-> azobis- (propionitrile)

i ^ i ⁰⁹ -14

Dimethyl 2-azobiisobubyrate l-azobis- (i-cyclohexanecarbonitrile) 2-Azob is- (2-methylheptanitr Ll) 2-AzobLb- (2-methylbutyron itr Ll) 4-azobis (4-cyanopentanoic acid) azodicarbonamide

Quinones, üxLme, etc.

p-Ghinon-d Loxime

p-DLbenzolylquinone-dioxime

2,6-dichloroquinone-chlorimine

Sulfur compounds

Benzothiazyl-d Lsulfide

Dibenzyl-disulfide

DLxylyl-d isulfide (various isomers)

2- (IIorpholinothio) benzothiyzole

Dibenzyl disulfide

Tetramethylth iuram-d isulfide

Uiphenyl disulfide

Di-p-tolyl diaulfide

Tetramethylthiuram monosulfide

BibtnzyIverbiη d ungen

CJ ^, ° C -dimebhoxy-o ^ oc ¹ -diphenylbibenzyl, cjC-diphenyl-i ^ x-methoxybibenzyl, o ^ -dimethoxy-oi, oC ¹ -d imethylbibenzyl, oC -dimethoxybibenzyl. 309810/0998

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Some or all of the particular embodiments described above can be so practiced be that one omits the organic peroxide and the reaction is carried out under conditions that have a partial thermal or oxidative decomposition of the polymer and / or the goreeactant to form free Radical leads. In addition, a third reactant can be used, the te access of oxygen without forms further free radicals, "for example an olefin, ether or thiol.

In the practice of this invention, it is contemplated that the reactive composition will usually be about 60-98% by weight polymer, about 1-30% by weight ooreactant, and about 1-20% by weight of a free radical initiator or contains a combination of initiators.

Additional materials such as PiO! Medium, pigment ^ dyes, plasticizers, foaming Agents and enhancing agents, etc. may be present during the reaction or added subsequently. It should be understood that such additives are not included in the percentage calculation given above Polymers, Goreactants and Initiator are included. In the practice of this invention, the reaction in a conventional vessel, for example in a chemical reactor, and the polymeric product can thereafter by conventional means such as

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For example, casting, extrusion, calendering, solution casting, etc. can be processed further.

Alternatively, the reaction mixture can be used as a film, coating, adhesive, three-dimensional object, etc. can be produced and processed, and the chemical reaction can subsequently be carried out in situ Heating, exposure to oxygen, etc. can be carried out.

The following examples illustrate some of the best embodiments contemplated by the inventor.

example 1

Ec was a solution of 30 gr. Polyethylene (Marlex TR 880), G g stearic acid and 3 g dieumyl peroxide in approx. ^ 50 N] hot xylene. By pouring on aliquots of this solution on warmed microscope slides were coated on glass substrates produced. After drying, the coatings became Heated to 135 over HachI in a vacuum oven.

The "cured" film shows good adhesion to glass. V / cnti ijoli'h a film (thickness ^C J mils = 0.2 mm) was peeled off and subjected to continuous extraction (Soathlet apparatus) under reflux with n-butanol not for ? <\ Seconds, the study of the IR spectrum shows, that the carboxyl-containing material (which comes from the stearic acid) by the extraction

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was not removed. When a physical mixture of polyethylene and stearic acid in the absence of Peroxides was prepared and treated similarly, the stearic acid was extracted by butanol removed.

Example 2

JiJs made a solution of 20g polyethylene (Marlex TR 880), 4g stearic acid and. 2g of dicumyl peroxide made in 400 ml of hot xylene. By pouring it on pilms were obtained. As such a PiIm between embedded in two layers of glass and this combination was heated to 145 for 4 hours, one formed firm adhesive bond.

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Example 3

A solution of 8 g of polyethylene (Microthene FN 500), 2 g oleic acid and 2 g 2,5 ~ dimethyl-2,5 bis (t-butylperoxy) hexyne-3 prepared in 80 ml of heated xylene and further processed to coatings by using the solution with a calibrated casting device on heated microscope slide poured out of glass. When such a coating was cured by constant heating to 170 ° C, it showed resulting coating has good adhesion to glass (which is due to an adhesive tape test). A sessile drop of distilled water formed a contact angle of 69 ° on the cured coating. Ftn additive-free polyethylene film manufactured and treated in the same way failed the adhesion test and had a water contact angle of 89 °.

Example ^

A series of covers were each made from 8.0 grams of polyethylene (Microthene FN 510), 2.0 g 2.5 ~ dimethyl ~ 2.5 ~ bis (t-butylperoxy) hexyne 3 and 2.0 g of a selected coreactant as described in Example 3 on a glass substrate. In the case the coreactants who followed showed the resulting coatings

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a strong adhesion to glass after being at 2 hours about 150 ° C had been cured; n-Dodecyltriethoxysi lan, sodium staaiat, sodium lauryl sulfate and cetyltrimethylammonium bromidο

Example 5

Parts of a solution of 8.0 g of ethylene vinyl acetate copolymer (Elvax 150, containing approx. 67% ethylene, 33 % vinyl acetate), 2.0 g of oleic acid and 2.5-dimethyl-2,5-bis (t -Butylperoxy) hexyne-3 in 80 ml of benzene were poured onto glass plates using a calibrated pouring device. After curing for 2 hours under nitrogen at approx. 160 ° C., these coatings passed the adhesive tape test for adhesion and showed water contact angles of approx. 40 °. Similarly behondf> 3rd tterzüge, v made of ethylene copolymer Vjnylacetat alone / aren ₉ failed beis tape test and showed V / as? ER = ~ ¥ Contact inkel of about 82 ° =

A pair of coatings., Made of S ₉ O g Ä acetal-Oepolyrnpr ("Elvax 420") _s containing approx. 82 $ £ Itliylon and 10 % vinyl acetate) ₉ 2.0 g 2 _i 5 "Dimethyl-2 ₉ 5" until-

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(t-butylperoxy) -hexane-3t and 2.0 g of a selected one Coreactants, prepared as described in Example 5, were prepared on a glass substrate. In the case of the following coreactants, the resulting coatings showed strong adhesion to glass after they had been cured for 2 hours at about 160 ° C.: "Dimer acid", sodium fearate. Cetyltrime thylammoni * · bromide.

In comparison with the starting polymers, the modified polymers produced according to the invention show a number of useful properties, These properties include increased susceptibility to degradation by environmental conditions, increased susceptibility to microbiological attack ("biodegradability"), improved Adhesion to surfaces such as metal, glass and wood, increased absorption capacity for dyes, paints and coatings, improved wetting of fillers, reinforcing agents and pigments, antistatic properties, improved emulsifiability and improved solubility in certain solvents.

Such properties suggest a wide variety of practical uses in areas such as for coatings, adhesives, packaging films, inks, plastic bowls and bottles, etc.

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Claims (15)

Claims Process for the production of chemically modified polyolefins or olefin copolymers, characterized in that a polyolefin or olefin copolymer is reacted with a coreactant which has both a hydrocarbon radical and at least one highly polar functional group in its structure, wherein this reaction is carried out in the presence of a source capable of generating free radicals in the presence of a suitable stimulant. 2. The method according to claim 1, characterized in that the coreactant is a non-polymeric organic compound of the general formula RX, where R is a linear, branched one or cyclic aliphatic hydrocarbon radical with at least 6 carbon atoms and X a polar one functional group is. 3. The method according to claim 1, characterized in that the co-reactant is a nonionic, anionic or cationic surfactant. 4. The method according to claim 1, characterized in that - 22 - 309810/0998 the coreactant is a fatty acid or a fatty acid amide. 5. The method according to claim 2, characterized in that the coreactant is a resin acid, an aliphatic dicarboxylic acid, is an aliphatic tricarboxylic acid, or salts thereof. 6. The method according to claim 1, characterized in that a polyolefin from the group consisting of polyethylene, polypropylene, Poly (1-butene) and poly (4-methyl-i-pentene) implemented will. 7. The method according to claim 1, characterized in that an olefin copolymer from the group ethylene-propylene copolymer, Ethylene-1-butene copolymer, ethylene-1-hexane copolymer, Ethylene-vinyl acetate copolymer, ethylene ethyl acrylate copolymer and ethylene-acrylic acid copolymer is reacted. 8. The method according to claim 1, characterized in that the source is an organic peroxide and the stimulus Warmth is. 9. The method according to claim 1, characterized in that the source is an azo compound and the stimulus is heat is. - 23 309810/0998 10. The method according to claim 1, characterized in that the source is a quinone oxime and the stimulus is heat. 11. The method according to claim 1, characterized in that the source is a sulfur compound and the stimulus is heat. 12. The method according to claim 1, characterized in that the source is a Bibenzsyl and the stimulus is heat. 13. The method according to claim 1, characterized in that the source is an organometallic compound, a hydroperoxide or a mixture thereof and the stimulus is heat. 14. The method according to claim 1, characterized in that the reaction carried out in situ on a substrate will. 15. Veriahren according to claim 1, characterized in that a mixture of the polymer or copolymer, the coraactant and the source into a suitable geometric shape Shaped and the reaction is carried out in situ while maintaining this geometric shape. 309810 / 099B ORIGINAL JNSPECTED